JP2019053228A - Pattern forming method and pattern forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming method and a pattern forming material capable of improving productivity. According to the embodiment, a pattern forming method and a contacting step are included. In the film forming step, a pattern forming material film containing the pattern forming material is formed on the substrate. The pattern-forming material includes a first portion and a second portion. The first portion comprises at least one of acrylate and methacrylate. The second portion comprises an aliphatic cyclic compound ester-bonded to the acrylate and at least one of the methacrylates, and a carbonyl group bonded to the aliphatic cyclic compound. In the pre-contact step, the pattern-forming material film is brought into contact with a metal compound containing a metal element. [Selection diagram] Fig. 1

Description

  Embodiments described herein relate generally to a pattern forming method and a pattern forming material.

  For example, there is a pattern forming material such as a resist material whose solubility is controlled by irradiation with ultraviolet rays or the like. In a pattern forming method and a pattern forming material having a pattern forming method using such a pattern forming material, improvement in productivity is required.

JP 2008-31160 A

  Embodiments of the present invention provide a pattern forming method and a pattern forming material capable of improving productivity.

  According to the embodiment of the present invention, a pattern forming method and a contact step are included. In the film forming step, a pattern forming material film including a pattern forming material is formed on the substrate. The pattern forming material includes a first portion and a second portion. The first portion includes at least one of acrylate and methacrylate. The second portion includes an aliphatic cyclic compound ester-bonded to the at least one of the acrylate and the methacrylate, and a carbonyl group bonded to the aliphatic cyclic compound. In the pre-contact step, the pattern forming material film is brought into contact with a metal compound containing a metal element.

FIG. 1A and FIG. 1B are schematic views illustrating pattern forming materials used in the pattern forming method according to the first embodiment. FIG. 2A to FIG. 2F are schematic cross-sectional views illustrating the pattern forming method according to the first embodiment. FIG. 3A to FIG. 3C are schematic views showing states in the pattern forming method.

Embodiments of the present invention will be described below with reference to the drawings.
The drawings are schematic or conceptual, and the relationship between the thickness and width of each part, the size ratio between the parts, and the like are not necessarily the same as actual ones. Even in the case of representing the same part, the dimensions and ratios may be represented differently depending on the drawings.
In the present specification and drawings, the same elements as those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description thereof is omitted as appropriate.

(First embodiment)
FIG. 1A and FIG. 1B are schematic views illustrating pattern forming materials used in the pattern forming method according to the first embodiment.
As shown in FIG. 1A, the pattern forming materials 110 and 111 include a first portion 10 and a second portion 20.

  In the example shown in FIG. 1A, the first portion 10 includes methacrylate. In the example shown in FIG.1 (b), the 1st part 10 contains an acrylate. In the embodiment, the first portion 10 includes at least one of acrylate and methacrylate.

  The second portion 20 includes an aliphatic cyclic compound 21 and a carbonyl group 22. The aliphatic cyclic compound 21 is ester-bonded with at least one of the acrylate and methacrylate of the first portion 20. For example, the aliphatic cyclic compound 21 is ester-bonded with at least one of the above acrylate and the above methacrylate directly or via an alkane having 1 to 3 carbon atoms. The carbonyl group 22 is bonded to the aliphatic cyclic compound 21.

  The aliphatic cyclic compound 21 may include, for example, a plurality of cyclic hydrocarbons bonded to each other. For example, the aliphatic cyclic compound 21 includes at least one selected from the group consisting of adamantane, tricyclodecane, isobornane, norbornane, and cyclohexane.

  The first portion 10 may include a side chain. For example, the side chain of the first portion 10 may include a carbonyl group 15. The carbonyl group 15 may be included in the ester group bond.

  The monomer containing the 1st part 10 and the 2nd part 20 is provided as a resist material by making it copolymerize with another acrylic compound, for example.

  For example, there is a case where a film of pattern forming material is used in a process in which a film of a pattern forming material is brought into contact with a metal compound containing a metal element. By using the above materials (such as the pattern forming materials 110 and 111), the metal compound can be effectively introduced into the film when the film of the pattern forming material is used in a process in which the film is brought into contact with the metal compound. . As a result, productivity can be improved as will be described later.

The pattern forming material according to the embodiment includes, for example, a composition represented by the following chemical formula.

  In the above chemical formula, “R1” is hydrogen or a methyl group. “R2” is an aliphatic cyclic compound (for example, an alicyclic compound). The aliphatic cyclic compound includes at least one selected from the group consisting of an adamantane ring, a tricyclodecane ring, an isobornane ring, a norbornane ring, a tetracyclododecane ring, and a cyclohexane ring. By using an aliphatic cyclic compound, for example, good dry etching resistance can be obtained. “R2” may be added with at least one selected from the group consisting of an alkyl group, a hydroxyl group, an amino group, and a carboxyl group.

  Hereinafter, an example of a pattern forming method using such materials (pattern forming materials 110 and 111 and the like) will be described. Below, the example using the pattern formation material 110 is demonstrated. The method described below is also applied when the pattern forming material 111 is used.

FIG. 2A to FIG. 2F are schematic cross-sectional views illustrating the pattern forming method according to the first embodiment.
As shown in FIG. 2A, a film 50 </ b> F including the pattern forming material 110 including the pattern forming material 110 is formed on the surface of the base body 60. For the formation of the film 50F, an arbitrary method such as a spinner method or an ink jet method is applied.

  As shown in FIG. 2A, an electromagnetic wave 45 is irradiated onto a part (first region R1) of the film 50F. For example, the electromagnetic wave 45 is irradiated to a part (first region R1) of the film 50F from the opening of the mask M1. Irradiation of the electromagnetic wave 45 may include scanning of the beam of the electromagnetic wave 45.

  Thereafter, for example, development is performed.

  As a result, as shown in FIG. 2B, the first region R1 irradiated with the electromagnetic wave 45 is removed. Thereby, the second region R2 of the film 50F remains. The second region R2 of the film 50F becomes the pattern forming material film 50.

  As described above, the pattern forming method according to the embodiment includes a film forming step of forming the pattern forming material film 50 including the pattern forming material 110 on the substrate 60. The film forming step includes, for example, a step of forming a film 50F including the pattern forming material 110 on the base body 60 (see FIG. 2A). The film forming step includes, for example, a step of irradiating the first region R1 of the film 50F with the electromagnetic wave 45 (see FIG. 2A).

  In the embodiment, the peak wavelength of the electromagnetic wave 45 is, for example, not less than 193 nm and less than 194 nm. For example, the electromagnetic wave 45 is emitted from an ArF excimer laser.

  The film forming step further includes a step of removing the first region R1 of the film 50F (see FIG. 2B). The pattern forming material film 50 (see FIG. 2B) is obtained from the remaining region (second region R2) of the film 50F.

  For example, in the step of removing the first region R1 of the film 50F (for example, development), for example, processing using an alkaline developer is performed. The alkaline developer includes, for example, TMAH (Tetramethylammonium hydroxide).

  As shown in FIG. 2C, the pattern forming material film 50 is brought into contact with the metal compound 30 containing the metal element 31.

The metal compound 30 includes, for example, an organometallic compound. The metal compound 30 includes, for example, trimethylaluminum. The metal compound 30 may include, for example, at least one selected from the group consisting of Ti, V, and W, and chlorine. For example, the metal compound 30 may include at least one selected from the group consisting of TiCl ₄ , VCl ₄ , and WCl ₆ .

  The metal compound 30 is, for example, a liquid or a gas.

  Thus, in the contact step, the pattern forming material film 50 is brought into contact with the metal compound 30 including the metal element 31. In the contact step, for example, the metal compound 30 is impregnated, for example, in the pattern forming material film 50. Thus, the contact step includes introducing the metal compound 30 into the pattern forming material film 50.

  For example, the contact step includes bringing the pattern forming material film 50 into contact with at least one of a liquid containing the metal compound 30 and a gas containing the metal compound 30. Thereby, for example, the metal element 31 included in the metal compound 30 is adsorbed to the material included in the pattern forming material film 50. This adsorption will be described later.

  As shown in FIG. 2D, after the contact step, the pattern forming material film 50 is processed in an atmosphere 62 containing at least one selected from the group consisting of water, oxygen, and ozone. This treatment includes heating. The heating temperature is, for example, 50 ° C. or higher and 180 ° C. or lower. In this processing step, for example, oxidation is performed.

As shown in FIG. 2E, after this processing step, the pattern forming material film 50 includes, for example, an oxide 32 including a metal element 31. For example, when the metal compound 30 includes trimethylaluminum, the oxide 32 including aluminum is formed. For example, when the metal compound 30 contains TiCl ₄ , an oxide 32 containing titanium is formed. For example, when the metal compound 30 contains VCl ₄ , an oxide 32 containing vanadium is formed. For example, when the metal compound 30 contains WCl ₆ , an oxide 32 containing tungsten is formed. For example, “metallization” is performed.

  When the oxide 32 is formed in the pattern forming material film 50, the etching resistance of the pattern forming material film 50 is improved. For example, the etching rate in dry etching using a gas containing chlorine is lowered.

  As shown in FIG. 2F, at least a part of the region of the substrate 60 that is not covered with the pattern forming material film 50 is removed after the above-described processing step (oxidation processing step). For example, etching using the pattern forming material film 50 as a mask is performed. This removal step includes, for example, contacting the uncovered region with a gas containing fluorine and carbon. Etching is, for example, RIE (Reactive Ion Etching).

  In the embodiment, the oxide 32 is formed in the pattern forming material film 50 as described above. For this reason, the etching resistance of the pattern forming material film 50 used as a mask is improved. Thereby, favorable workability is obtained in the etching (the above-described removal step) using the pattern forming material film 50 as a mask. High precision machining can be performed.

  According to the embodiment, a pattern forming method capable of improving productivity can be provided.

  For example, in the etching process, good processability can be obtained even when the line width is 100 nm or less. For example, the width W1 of at least a part of the region not covered with the pattern forming material film 50 is 100 nm or less. The width W <b> 1 is a width along one direction (first direction) along the base body 60.

  Hereinafter, an example of the bond between the metal element 31 included in the metal compound 30 and the material included in the pattern forming material film 50 will be described.

FIG. 3A to FIG. 3C are schematic views showing states in the pattern forming method.
These drawings illustrate the case where the first portion 10 of the pattern forming material 110 includes methacrylate. The metal compound 30 is trimethylaluminum, and the metal element 31 is aluminum.

  In the first state shown in FIG. 3A, the metal element 31 (aluminum) is adsorbed (or bonded) to the carbonyl group 22 of the aliphatic cyclic compound 21.

  On the other hand, in the second state shown in FIG. 3B, the metal element 31 (aluminum) is adsorbed (or bonded) to the carbonyl group 15 in the side chain of the acrylate.

  For these states, the stabilization energy ΔE is calculated based on molecular orbital calculation (GAUSSIUN etc.) using the first principle. As a result, the stabilization energy ΔE in the first state is −18.28 kcal / mol. On the other hand, the stabilization energy ΔE in the second state is −14.73 kcal / mol. Thus, it was found from this calculation that the first state is more stable than the second state.

  In the third state shown in FIG. 3 (c), the metal element 31 (aluminum) is adsorbed at two locations of the carbonyl group 22 of the aliphatic cyclic compound 21 and the carbonyl group 15 of the ester portion of the acrylate (or Join. The stabilization energy ΔE in the third state is −32.21 kcal / mol. In this value, the stabilization energy ΔE in the third state is substantially equal to the sum of the first state and the second state. This means that another metal element 31 is easily adsorbed even after the metal element 31 is adsorbed in the first state or the second state. That is, the adsorption capacity of the metal element 31 per segment is simply doubled.

  This means that the metal element 31 (aluminum) can be more efficiently taken into the pattern forming material film 50 by providing the alicyclic compound 21 with the carbonyl group 22.

The phenomenon described here also occurs in other metal compounds other than trimethylaluminum. For example, the same thing occurs with TiCl ₄ , WCl ₆ , and VCl ₄ .

  For example, a pattern forming material of a reference example in which the carbonyl group 22 of the aliphatic cyclic compound 21 is not provided is conceivable. In this case, only the second state is formed.

  In contrast, in the embodiment, the alicyclic compound 21 is provided with a carbonyl group 22. Thereby, compared with said reference example, the metal element 31 (aluminum) can be taken in into the pattern formation material film 50 with high efficiency. Thereby, the concentration of the oxide containing the metal element 31 in the pattern forming material film 50 can be further increased by the above-described treatment process (for example, the oxidation process).

  Thus, in the embodiment, after the contacting step, the metal element 31 is adsorbed on the carbonyl group 22 bonded to the aliphatic cyclic compound 21. For example, the first state is formed.

  In the embodiment, the second state may be formed in addition to the first state. For example, after the contact step, the metal element 31 may be adsorbed on the carbonyl group 15 contained in at least one of acrylate and methacrylate.

(Second Embodiment)
The second embodiment relates to a pattern forming material.
The pattern forming material (pattern forming material 110 or 111) according to the embodiment includes a first portion 10 including at least one of acrylate and methacrylate, and a second portion 20 (FIG. 1A and FIG. 1). b)). The second portion 20 includes an aliphatic cyclic compound 21 and a carbonyl group 22. The aliphatic cyclic compound 21 is ester-bonded to at least one of the above acrylate and the above methacrylate. The carbonyl group 22 is bonded to the aliphatic cyclic compound 21. This pattern forming material is used in a pattern forming method including a step in which a film containing the pattern forming material (for example, the pattern forming material film 50) is brought into contact with the metal compound 30 containing the metal element 31.

  According to the pattern forming material according to the embodiment, for example, a pattern forming material having high etching resistance can be provided. For example, a pattern forming material capable of improving productivity can be provided.

The embodiment may include the following configuration (technical proposal).
(Configuration 1)
A first portion containing at least one of acrylate and methacrylate; and a second portion, wherein the second portion is an aliphatic cyclic compound ester-bonded to the at least one of the acrylate and the methacrylate, and the aliphatic cyclic. A film forming step of forming a pattern forming material film including a pattern forming material including a second portion including a carbonyl group bonded to a compound on a substrate;
Contacting the pattern forming material film with a metal compound containing a metal element;
A pattern forming method comprising:
(Configuration 2)
The film forming step includes
Forming a film containing the pattern forming material on the substrate;
Irradiating the first region of the film with electromagnetic waves;
Removing the first region of the film;
Including
The pattern forming method according to Configuration 1, wherein the pattern forming material film is obtained from a region where the film remains.
(Configuration 3)
The pattern forming method according to Configuration 2, wherein a peak wavelength of the electromagnetic wave is less than 194 nm.
(Configuration 4)
The pattern forming method according to Configuration 2 or 3, wherein the electromagnetic wave is emitted from an ArF excimer laser.
(Configuration 5)
The pattern forming method according to any one of configurations 1 to 4, wherein the contacting step includes introducing the metal compound into the pattern forming material film.
(Configuration 6)
The pattern formation according to any one of configurations 1 to 5, wherein the contacting step includes bringing the pattern forming material film into contact with at least one of a liquid containing the metal compound and a gas containing the metal compound. Method.
(Configuration 7)
The said metal element adsorb | sucks to the said carbonyl group couple | bonded with the said aliphatic cyclic compound after the said contact process, The pattern formation method as described in any one of the structures 1-6.
(Configuration 8)
The pattern forming method according to any one of configurations 1 to 6, wherein the metal element is adsorbed to a carbonyl group contained in at least one of the acrylate and the methacrylate after the contact step.
(Configuration 9)
Any one of configurations 1 to 8, further comprising a treatment step of treating the pattern forming material film in an atmosphere including at least one selected from the group consisting of water, oxygen, and ozone after the contact step. The pattern formation method as described in one.
(Configuration 10)
The pattern formation method according to Configuration 9, wherein after the processing step, the pattern formation material film includes an oxide containing the metal element.
(Configuration 11)
The pattern forming method according to any one of Structures 1 to 10, further comprising a removing step of removing at least a part of the region of the substrate not covered with the pattern forming material film after the processing step.
(Configuration 12)
The pattern forming method according to Configuration 11, wherein the removing step includes bringing the uncovered region into contact with a gas containing fluorine and carbon.
(Configuration 13)
The pattern forming method according to Configuration 11 or 12, wherein a width of at least a part of the uncovered region along the first direction along the base is 100 nm or less.
(Configuration 14)
The said metal compound is a pattern formation method as described in any one of the structures 1-13 containing an organometallic compound.
(Configuration 15)
The pattern formation method according to any one of configurations 1 to 13, wherein the metal compound includes trimethylaluminum.
(Configuration 16)
The pattern forming method according to any one of configurations 1 to 7, wherein the metal compound includes at least one selected from the group consisting of Ti, V, and W and chlorine.
(Configuration 17)
The said aliphatic cyclic compound is a pattern formation method as described in any one of the structures 1-16 containing the some cyclic hydrocarbon couple | bonded together.
(Configuration 18)
The aliphatic cyclic compound includes at least one selected from the group consisting of an adamantane ring, a tricyclodecane ring, an isobornane ring, a norbornane ring, a tetracyclododecane ring, and a cyclohexane ring, and any one of configurations 1 to 17 The pattern forming method according to 1.
(Configuration 19)
The first portion includes a side chain;
The pattern formation method according to any one of configurations 1 to 18, wherein the aliphatic cyclic compound is bonded to the side chain.
(Configuration 20)
A first portion comprising at least one of acrylate and methacrylate;
The second part, wherein the second part includes an aliphatic cyclic compound ester-bonded to the at least one of the acrylate and the methacrylate, and a carbonyl group bonded to the aliphatic cyclic compound. When,
A pattern forming material comprising:
The pattern formation material used for the pattern formation method including the process by which the film | membrane containing the said pattern formation material is made to contact the metal compound containing a metal element.

  According to the embodiment, a pattern forming method and a pattern forming material capable of improving productivity can be provided.

  The embodiments of the present invention have been described above with reference to specific examples. However, the present invention is not limited to these specific examples. For example, regarding a specific configuration of each element such as an acrylate, a methacrylate, an aliphatic cyclic compound, and the like included in the pattern forming material, a person skilled in the art may use the pattern forming material, metal element, and metal compound used in the pattern forming method. The present invention is similarly implemented by appropriately selecting from known ranges, and is included in the scope of the present invention as long as similar effects can be obtained.

  Moreover, what combined any two or more elements of each specific example in the technically possible range is also included in the scope of the present invention as long as the gist of the present invention is included.

  In addition, all pattern forming methods and pattern forming materials that can be implemented by those skilled in the art based on the pattern forming methods and pattern forming materials described above as embodiments of the present invention are also included in the gist of the present invention. As long as it is included, it belongs to the scope of the present invention.

  In addition, in the category of the idea of the present invention, those skilled in the art can conceive of various changes and modifications, and it is understood that these changes and modifications also belong to the scope of the present invention. .

  Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  DESCRIPTION OF SYMBOLS 10 ... 1st part, 15 ... Carbonyl group, 20 ... 2nd part, 21 ... Aliphatic cyclic compound, 22 ... Carbonyl group, 30 ... Metal compound, 31 ... Metal element, 32 ... Oxide, 45 ... Electromagnetic wave, 50 ... Pattern forming material film, 50F ... film, 60 ... substrate, 62 ... atmosphere, 110, 111 ... pattern forming material, M1 ... mask, R1 ... first region, R2 ... second region, W1 ... width

Claims (11)

A first portion containing at least one of acrylate and methacrylate; and a second portion, wherein the second portion is an aliphatic cyclic compound ester-bonded to the at least one of the acrylate and the methacrylate, and the aliphatic cyclic. A film forming step of forming a pattern forming material film including a pattern forming material including a second portion including a carbonyl group bonded to a compound on a substrate;
Contacting the pattern forming material film with a metal compound containing a metal element;
A pattern forming method comprising: The film forming step includes
Forming a film containing the pattern forming material on the substrate;
Irradiating the first region of the film with electromagnetic waves;
Removing the first region of the film;
Including
The pattern forming method according to claim 1, wherein the pattern forming material film is obtained from a region where the film remains.   The pattern formation method according to claim 2, wherein a peak wavelength of the electromagnetic wave is less than 194 nm.   The pattern forming method according to claim 1, wherein the contacting step includes introducing the metal compound into the pattern forming material film.   The pattern according to any one of claims 1 to 4, wherein the contact step includes bringing the pattern forming material film into contact with at least one of a liquid containing the metal compound and a gas containing the metal compound. Forming method.   The process according to any one of claims 1 to 5, further comprising a treatment step of treating the pattern forming material film in an atmosphere containing at least one selected from the group consisting of water, oxygen, and ozone after the contact step. The pattern formation method as described in one.   The pattern formation method according to claim 6, wherein after the treatment step, the pattern formation material film includes an oxide containing the metal element.   The pattern forming method according to claim 1, further comprising a removing step of removing at least a part of a region of the substrate that is not covered with the pattern forming material film after the processing step. .   The pattern formation method according to claim 1, wherein the metal compound includes an organometallic compound.   The pattern forming method according to claim 1, wherein the metal compound includes at least one selected from the group consisting of Ti, V, and W, and chlorine. A first portion comprising at least one of acrylate and methacrylate;
The second part, wherein the second part includes an aliphatic cyclic compound ester-bonded to the at least one of the acrylate and the methacrylate, and a carbonyl group bonded to the aliphatic cyclic compound. When,
A pattern forming material comprising:
The pattern formation material used for the pattern formation method including the process by which the film | membrane containing the said pattern formation material is made to contact the metal compound containing a metal element.

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